CN108531729A - A kind of vanadium iron separation method containing vanadium solution - Google Patents

Abstract

The present invention relates to a kind of vanadium iron separation method containing vanadium solution.Its technical solution is：By Potassium In Potassium ion: the amount ratio containing the substance of iron ion in vanadium solution is (1~6): 1, sylvite addition is described containing in vanadium solution, 1~3h, liquid after being reacted are stirred under the conditions of 80~95 DEG C.Liquid after the reaction stands at 0~10 DEG C and under the conditions of be protected from light to 3~for 24 hours, it is separated by solid-liquid separation, obtains liquid and filter cake after vanadium iron separation；Liquid is used for the further purification enrichment of vanadium after the vanadium iron separation；The filter cake is used for potassium ferric oxalate (K₃[Fe(C₂O₄)₃]·3H₂O) further purification.It is described to contain vanadium solution：A concentration of 1~4g/L of vanadium；Concentration of iron is 3~10g/L；A concentration of 10~30g/L of oxalate；PH value is 0~5.The sylvite is one or more of potassium chloride, potassium sulfate, potassium oxalate, potassium nitrate.Present invention process is simply and at low cost, has vanadium iron good separating effect, comprehensive resource utilization rate high and environmental benefit outstanding feature.

Description

A kind of vanadium-iron separation method of vanadium-containing solution

technical field

The invention belongs to the technical field of vanadium iron separation. Specifically, it relates to a method for separating ferrovanadium from a vanadium-containing solution.

Background technique

Usually, the vanadium-containing solution contains more impurity iron ions. The presence of iron ions will affect the subsequent purification and enrichment process of vanadium and the quality of the final vanadium product. Therefore, it is necessary to separate vanadium-iron from the vanadium-containing solution.

The separation methods of ferrovanadium in vanadium-containing solution mainly include neutralization method, extraction method and precipitation method. The neutralization method mainly realizes the separation of vanadium and iron by adding alkali to precipitate iron in the form of ferric hydroxide; the extraction method is to extract vanadium by adding an extractant to the vanadium-containing solution without extracting iron to realize the separation of vanadium and iron; the crystallization method is mainly By adding a reducing agent such as iron powder, the ferric iron in the solution is reduced to ferrous iron, and then reacts with oxalate to form ferrous oxalate crystals to realize the separation of ferrovanadium.

"A method for removing iron from vanadium-containing stone coal leaching liquid" (CN 105695738A) patent technology, the vanadium-containing stone coal is crushed, roasted, and ground to obtain vanadium-containing stone coal calcine, and the vanadium-containing stone coal calcine is mixed with water , to obtain vanadium-containing stone coal slurry, then add leaching agent, heat and stir, and separate solid and liquid to obtain vanadium-containing stone coal leachate and leaching slag; add reduced iron powder to vanadium-containing stone coal leachate, adjust the pH to 1.5-5, Heating and stirring, solid-liquid separation, leachate and filter cake after iron removal are obtained; the by-product of ferrous oxalate dihydrate is obtained after the filter cake is dried. Although the invention can effectively separate vanadium and iron in the vanadium-containing stone coal leach solution, the vanadium loss rate is low and the iron removal rate is high, but the iron removal process is complicated and the process is long. The iron powder is used as the reducing agent in the iron removal process, which will lead to The ion content increases, and its essence is to realize the separation of vanadium and iron by the by-product of ferrous oxalate, but the price of ferrous oxalate industrial products is about 10,000 yuan/ton, which is far lower than the price of ferrous potassium oxalate industrial products (25,000-30,000 yuan/ton tons), which is not conducive to production applications.

Two-step solvent extraction for iron removal (Yiqian Ma, Xuewen Wang, Mingyu Wang, et.al.Separation of V(IV) and Fe(III) from the acid leach solution of stone coal by D2EHPA/TBP[J].Hydrometallurgy,2015 (153):38～45), which is to remove iron by two-step solvent extraction method for the leachate containing V(Ⅳ) 2.87g/L, Fe(Ⅲ) 8.45g/L and Fe(Ⅱ) 2.71g/L The first step is to use D2EHPA/TBP extractant to remove ferric iron in the vanadium-containing solution. After the iron removal, the solution is adjusted to pH and then the D2EHPA/TBP extractant is used to enrich the vanadium. The Fe(Ⅲ) removal rate of this process is up to About 90%; Although the two-step solvent extraction method can separate vanadium and iron in the acid leaching solution, the separation process is complicated, the consumption of chemicals is large, the cost is high, and there is no recovery of iron resources.

Qi Dong (Qi Dong, Wang Yi. Exploration on Iron Removal Process of Vanadium-Containing Leaching Solution[J]. Nonferrous Mining and Metallurgy, 2015, 31(3): 37-39) on the effect of iron removal in direct acid leaching solution of stone coal materials in a certain place The process was explored. Lime was used to neutralize the vanadium-containing acid leaching solution, and the pH was controlled to be about 2. Then, iron filings were added to reduce Fe ³⁺ to Fe ²⁺ , and V ⁵⁺ to V ⁴⁺ , and then P204 was used for extraction. Vanadium is extracted with a solvent to form a "neutralization-reduction-solvent extraction" joint treatment technology. The final iron removal rate reaches more than 99%, and the vanadium recovery rate reaches more than 80%. Although the separation effect of ferrovanadium by this method is good, the process flow is long, there are many types of chemicals, the amount of chemicals is large, the cost is high, and there is no recovery of iron resources.

Looking at the status quo of the separation methods of vanadium and iron in vanadium-containing solutions at home and abroad, the extraction method is mainly used to separate vanadium and iron, and the vanadium is selectively extracted by the extractant, and the iron is not extracted to realize the separation of vanadium and iron. However, the extraction process is complicated, and back-extraction is required after extraction. Although ferrovanadium is separated, the separated raffinate still contains a large amount of iron impurities, which cannot be discharged directly, and still need to be reprocessed.

Contents of the invention

The invention aims to overcome the defects of the prior art, and aims to provide a method for separating vanadium and iron from a vanadium-containing solution with simple process, low cost, good separation effect of vanadium and iron, high resource comprehensive utilization rate and remarkable environmental protection benefit.

In order to achieve the above object, the technical scheme adopted in the present invention is:

(1) According to the potassium ion in the potassium salt: the material ratio of the iron ion in the vanadium-containing solution is (1～6): 1, the potassium salt is added in the described vanadium-containing solution, and stirred at 80～95° C. 1 ~ 3h, to obtain the liquid after the reaction.

(2) the liquid after the reaction is left standing for 3 to 24 hours at 0 to 10 DEG C and light-proof conditions, and the solid and liquid are separated to obtain the liquid and filter cake after the separation of vanadium and iron; the liquid after the separation of vanadium and iron is used for vanadium Further purification and enrichment; the filter cake is used for further purification of ferric potassium oxalate.

The vanadium-containing solution: the concentration of vanadium is 1-4g/L; the concentration of iron is 3-10g/L; the concentration of oxalate is 10-30g/L; the pH value is 0-5.

The potassium salt is more than one of potassium chloride, potassium sulfate, potassium oxalate and potassium nitrate.

Owing to adopting above-mentioned technical scheme, the present invention has following positive effect compared with prior art:

1. The present invention realizes the separation of vanadium and iron by adding potassium salt in the vanadium-containing solution, and placing it under low temperature and light-proof environment after heating and stirring, to precipitate crystals, and obtain the liquid after separation of vanadium and iron, which is used for For further enrichment of vanadium, the process is simple and the cost is low.

2. The present invention can not only effectively separate vanadium and iron in the vanadium-containing solution, but also make full use of the impurity iron ions in the solution, turn waste into treasure, and obtain a filter cake, which is used for ferric potassium oxalate (K ₃ [ Fe(C ₂ O ₄ ) ₃ ] · 3H ₂ O) is further purified, no waste liquid and waste residue are produced in the separation process, the comprehensive utilization rate of resources is improved, and the environmental protection benefit is remarkable.

3. The vanadium-containing solution adopted in the present invention: the vanadium concentration is 1-4g/L, the iron concentration is 3-10g/L, the oxalate concentration is 10-30g/L, and the pH value is 0-5; The solution after the separation of vanadium and iron: the vanadium concentration is 1-4g/L, the iron concentration is only 0.5-1.2g/L, the iron removal rate is 80-90%, and the vanadium loss rate is lower than 2% during the iron removal process; The vanadium loss rate is low, the iron removal rate is high, and the separation effect of vanadium and iron is good. The liquid after separation is conducive to the further enrichment of vanadium.

Therefore, the invention has simple process and low cost, and has the characteristics of good separation effect of vanadium and iron, high comprehensive resource utilization rate and remarkable environmental protection benefit.

Detailed ways

The present invention will be further described below in conjunction with specific embodiment, is not the restriction of its protection scope:

In order to avoid repetition, the potassium salt in this specific embodiment is firstly described as follows, and will not be repeated in the examples.

The potassium salt is more than one of potassium chloride, potassium sulfate, potassium oxalate and potassium nitrate.

Example 1

The invention discloses a method for separating ferrovanadium from a vanadium-containing solution. The vanadium-containing solution described in this embodiment is: the concentration of vanadium is 1-2 g/L; the concentration of iron is 3-6 g/L; the concentration of oxalate is 10-20 g/L; the pH value is 2-5.

The iron-vanadium separation method of the vanadium-containing solution described in the present embodiment is:

(1) According to the potassium ion in the potassium salt: the material ratio of the iron ion in the vanadium-containing solution is (1～4): 1, the potassium salt is added in the described vanadium-containing solution, and stirred at 80～85° C. 1 ~ 3h, to obtain the liquid after the reaction.

(2) the liquid after the reaction is left to stand for 3 to 10 hours at 0 to 10° C. and under light-proof conditions, and the solid and liquid are separated to obtain the liquid and filter cake after the separation of vanadium and iron; the liquid after the separation of vanadium and iron is used for Further purification and enrichment; the filter cake is used for further purification of ferric potassium oxalate.

The liquid after separation of vanadium and iron obtained in this embodiment: the concentration of vanadium is 1-2 g/L; the concentration of iron is 0.5-0.8 g/L. In this embodiment, the iron removal rate is 90-95%, and the vanadium loss rate is lower than 2%.

Example 2

The invention discloses a method for separating ferrovanadium from a vanadium-containing solution. The vanadium-containing solution described in this embodiment is: the concentration of vanadium is 2-3 g/L; the concentration of iron is 5-8 g/L; the concentration of oxalate is 15-25 g/L; the pH value is 1-4.

The iron-vanadium separation method of the vanadium-containing solution described in the present embodiment is:

(1) According to the potassium ion in the potassium salt: the material ratio of the iron ion in the vanadium-containing solution is (2～5): 1, the potassium salt is added in the described vanadium-containing solution, and stirred at 85～90°C 1 ~ 3h, to obtain the liquid after the reaction.

(2) the liquid after the reaction is left standing for 10 to 16 hours at 0 to 10 DEG C and light-proof conditions, and the solid and liquid are separated to obtain the liquid and filter cake after the separation of vanadium and iron; the liquid after the separation of vanadium and iron is used for vanadium Further purification and enrichment; the filter cake is used for further purification of ferric potassium oxalate.

The liquid after separation of vanadium and iron obtained in this embodiment: the concentration of vanadium is 2-3 g/L; the concentration of iron is 0.7-1.0 g/L. In this embodiment, the iron removal rate is 87-92%, and the vanadium loss rate is lower than 2%.

Example 3

The invention discloses a method for separating ferrovanadium from a vanadium-containing solution. The vanadium-containing solution described in this embodiment is: the concentration of vanadium is 3-4 g/L; the concentration of iron is 7-10 g/L; the concentration of oxalate is 20-30 g/L; the pH value is 0-3.

The iron-vanadium separation method of the vanadium-containing solution described in the present embodiment is:

(1) According to the potassium ion in the potassium salt: the material ratio of the iron ion in the vanadium-containing solution is (3～6): 1, the potassium salt is added in the described vanadium-containing solution, and stirred at 90～95° C. 1 ~ 3h, to obtain the liquid after the reaction.

(2) the liquid after the reaction is left standing for 16 to 24 hours at 0 to 10 DEG C and light-proof conditions, and the solid and liquid are separated to obtain the liquid and filter cake after the separation of vanadium and iron; the liquid after the separation of vanadium and iron is used for vanadium Further purification and enrichment; the filter cake is used for further purification of ferric potassium oxalate.

The liquid after separation of vanadium and iron obtained in this embodiment: the concentration of vanadium is 3-4 g/L; the concentration of iron is 0.9-1.2 g/L. In this embodiment, the iron removal rate is 85-90%, and the vanadium loss rate is lower than 2%.

Compared with the prior art, this specific embodiment has the following positive effects:

1. This specific embodiment is by adding potassium salt in the vanadium-containing solution, after being heated and stirred, it is placed under low temperature and light-proof environment, and crystals are precipitated, and the separation of vanadium and iron is realized, and the liquid after the separation of vanadium and iron is obtained, and the liquid after the separation of vanadium and iron For further enrichment of vanadium, the process is simple and the cost is low.

2. this embodiment not only can effectively separate vanadium and iron in the vanadium-containing solution, but also can make full use of the impurity iron ions in the solution, turn waste into treasure, and obtain filter cake, and described filter cake is used for ferric potassium oxalate (K ₃ [Fe(C ₂ O ₄ ) ₃ ]·3H ₂ O) is further purified, no waste liquid and waste residue are generated during the separation process, the comprehensive utilization rate of resources is improved, and the environmental protection benefit is remarkable.

3. the vanadium-containing solution that this specific embodiment adopts: vanadium concentration is 1～4g/L, and iron concentration is 3～10g/L, and oxalate root concentration is 10～30g/L, and pH value is 0～5; Separation of ferrovanadium after separation: the vanadium concentration is 1-4g/L, the iron concentration is only 0.5-1.2g/L, the iron removal rate is 80-90%, and the vanadium loss rate is less than 2% during the iron removal process . Therefore, this specific embodiment has low vanadium loss rate, high iron removal rate and good separation effect of vanadium and iron, and the liquid after separation is beneficial to the further enrichment of vanadium.

Therefore, this specific embodiment has simple process and low cost, and has the characteristics of good separation effect of vanadium and iron, high comprehensive resource utilization rate and remarkable environmental protection benefit.

Claims (2)

1. a ferrovanadium separation method containing vanadium solution, it is characterized in that described ferrovanadium separation method is: (1) According to the potassium ion in the potassium salt: the material ratio of the iron ion in the vanadium-containing solution is (1～6): 1, the potassium salt is added in the described vanadium-containing solution, and stirred at 80～95° C. 1～3h, get the liquid after reaction; (2) placing the reacted liquid at 0-10° C. and under the condition of avoiding light for 3-24 hours, and separating the solid and liquid to obtain the separated liquid and filter cake of ferrovanadium; The liquid after the separation of vanadium and iron is used for further purification and enrichment of vanadium; the filter cake is used for further purification of ferric potassium oxalate; The vanadium-containing solution: the vanadium concentration is 1-4g/L, the iron concentration is 3-10g/L, the oxalate concentration is 10-30g/L, and the pH value is 0-5. 2. according to the described ferrovanadium separation method of vanadium-containing solution of claim 1, it is characterized in that described potassium salt is more than one in potassium chloride, potassium sulfate, potassium oxalate, potassium nitrate.